CN103996813A - Preparation method and device of bi-directional reinforced electrostatic spinning lithium ion battery diaphragm - Google Patents
Preparation method and device of bi-directional reinforced electrostatic spinning lithium ion battery diaphragm Download PDFInfo
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- CN103996813A CN103996813A CN201410241350.7A CN201410241350A CN103996813A CN 103996813 A CN103996813 A CN 103996813A CN 201410241350 A CN201410241350 A CN 201410241350A CN 103996813 A CN103996813 A CN 103996813A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/74—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being orientated, e.g. in parallel (anisotropic fleeces)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a preparation method and device of a bi-directional reinforced electrostatic spinning lithium ion battery diaphragm. The bi-directional reinforced electrostatic spinning lithium ion battery diaphragm is characterized in that the diaphragm is a three-layer composite fibrous membrane and is formed in an electrostatic spinning device adopting a parallel electrode as a receiving end. The upper layer and the lower layer are respectively an irregular orientation fibrous membrane and are prepared by the parallel electrode which stays at a rotating state on the plane on which the electrode stays, an intermediate layer is a cross orientation fibrous membrane and is prepared by adopting the parallel electrode to receive for a period of time at a stationary state and receive for a period of time at a stationary state after rotating for 90 degrees along the plane on which the electrode stays. The porosity of the diaphragm reaches up to 55 to 85 percent, and the tensile breaking strength in the longitudinal and transverse direction is improved by 100 to 400 percent compared with the irregular orientation fibrous membrane. The preparation process can be completed on one electrostatic spinning device, so that the continuous production of the composite diaphragm can be realized, and the process is simple, easy to control, convenient to operate and low in cost.
Description
Technical field
The present invention relates to lithium ion battery separator field, particularly relate to that a kind of mechanical strength is good, porosity is high, the two-way enhancement mode Static Spinning lithium ion battery separator of Heat stability is good preparation method and device.
Background technology
Compare the advantage such as lithium ion battery has that voltage is high, specific energy is high, discharges and recharges life-span length, memory-less effect, environmental pollution are little, quick charge, self-discharge rate are low with other rechargeable batteries.Therefore, lithium ion battery gets more and more and is applied to fields such as mobile phone, notebook computer, electric bicycle and power vehicle.Lithium battery is mainly comprised of positive pole, negative pole, electrolyte, barrier film and shell etc.Wherein, barrier film is a very important part, and it is the perforated membrane of a kind of ion conducting, electronic isolation, plays the effect of isolation between positive pole and negative pole, to prevent internal short-circuit of battery.Therefore, require battery diaphragm must possess the features such as good insulation preformance, porosity is high, mechanical property good, chemical stability is excellent.
Application at present more widely commercialization barrier film is microporous polyolefin film, adopt of its preparation method melt extrudes TPO material more, make it form semi-crystalline polymer film, then film is carried out to unidirectional or biaxial tension, make film surface form long and narrow micropore, and make it on unidirectional or two-way, there is good mechanical performance, thereby make battery diaphragm.Yet this barrier film complex manufacturing, pore-size distribution is irregular, porosity is lower, absorbent is poor, is unfavorable for the migration of lithium ion in lithium ion battery charge and discharge process.In addition, polyolefin battery separation film surface can be low, causes film poor to the wetting property of electrolyte, and this reduces the overall performance of battery and fail safe.
Electrostatic spinning refers under electrostatic field a kind of spining technology that polymer solution or melt is drawn into fiber.Fibre diameter prepared by the method is that nanoscale, specific area are large, and resulting barrier film has that porosity is high, aperture is little and even, imbibition and guarantor's fluidity can good, ionic conductivity advantages of higher, are generally acknowledged high performance lithium ion battery diaphragm materials.Although the nanofiber battery diaphragm that adopts electrospinning process to prepare has above-mentioned advantage, Static Spinning battery diaphragm is to be overlapped and form mutually by mixed and disorderly fiber, and mechanical performance is poor, does not many times all reach the intensity of assembled battery.
In current disclosed scale, prepare in the pertinent literature technology of device of Static Spinning lithium ion battery separator; as: patent CN101192681A has designed a kind of equipment of continuous production electrostatic spinning fiber film, and on lithium ion cell electrode sheet surface, directly prepares composite nano fiber barrier film with this equipment.This equipment has been reformed lithium ion battery tradition assembly technology, but this equipment is but for the preparation of strengthening barrier film.Patent US6713011B2 has recorded a kind of apparatus and method of utilizing electrostatic spinning process to weave barrier film, and adopt these apparatus and method to carry out continuous industry production, the membrane for polymer film forming of gained is inhomogeneous, way contracting is more, can not be for the preparation of lithium ion battery separator.
At present in disclosed enhancement mode Static Spinning battery diaphragm pertinent literature technology, as: patent CN102140734A prepares fluoropolymer resin and base polyurethane prepolymer for use as bicomponent fibers film by electrostatic spinning technique, because base polyurethane prepolymer for use as crosslinked, the auto polymerization reaction that reacts generates polyurethane, make it with tunica fibrosa in polymer form half interpenetrating network structure, improved the mechanical strength of tunica fibrosa.Yet base polyurethane prepolymer for use as, with the isocyanate group group of high reaction activity, makes it be subject to the impact of moisture etc., the storage life is shorter.Patent CN101974828A electrostatic spinning obtains copolyamide acid nano-fiber for production of non-woven, and at high temperature carries out imidization, prepares the barrier film that mechanical strength is higher.Yet, under hot conditions, can not effectively control polyester-polyamide acid imide degree, therefore, the barrier film of preparation does not have replicability, and performance also has otherness.Patent CN103469488A has prepared two kinds of melt temperatures and has differed 30 ℃ of above polymer Static Spinning blended fiber films, through hot rolling, processes, and the nanofiber in tunica fibrosa is bondd each other, thereby improves the mechanical strength of tunica fibrosa.But low melting point composition melting under hot-rolled condition in barrier film prepared by the method, reduces tunica fibrosa porosity, pick up, is unfavorable for the migration of lithium ion, so barrier film ionic conductivity can reduce, and affects cycle performance of battery.Patent US20120077015A1 presss from both sides one deck nanofiber film preparation MULTILAYER COMPOSITE nano composite material between two supporting layers, as lithium ion battery separator.Though this barrier film mechanical performance obviously improves, but barrier film porosity is lower, thickness is larger, increases the internal resistance of battery.(the Wu YP such as Zhu, Zhu Y, Xiao S, et al.A trilayer poly (vinylidene fluoride)/polyborate/poly (vinylidene fluoride) gel polymer electrolyte with good performance for lithium ion batteries[J] .Journal of Materials Chemistry A, 2013.) thickness being about to 25 μ m LiPAAOB cast membrane is placed in on the wetting Static Spinning pvdf membrane of ethanol/water, place after cast membrane, layer overlay Static Spinning pvdf membrane in cast membrane again, work as ethanol, water has just been prepared sandwich diaphragm after being heated and volatilizing, intermediate layer is coated film, skin is tunica fibrosa.This film mechanical strength improves, but applies or the uniform dielectric substrate of the difficult formation of dipping, affects electrode/electrolyte interface character, thereby affects the performance of battery.
Also have and in some other patented technologies or document, mention the tunica fibrosa that uses Static Spinning technology to prepare right-angled intersection orientations, but be not applied in battery diaphragm, as: patent WO2013066269A1 has introduced and has utilized ground connection flywheel to receive the Ni tunica fibrosa that obtains right-angled intersection orientations, and for the growth of Graphene, through curing process, peel off Ni fiber, form the self-supporting Graphene electrodes with right-angled intersection pattern.(the Wu S such as Wu, Tai Q, Yan F.Hybrid photovoltaic devices based on poly (3-hexylthiophene) and ordered electrospun ZnO nanofibers[J] .The Journal of Physical Chemistry C, 2010,114 (13): cancellated zinc oxide (ZnO) nanofiber of right-angled intersection 6197-6200.) obtaining, and as intermediate layer, yet final products are to be but applied in photovoltaic apparatus---in solar cell.(the Cho S J such as Cho, Kim B, An T, et al.Replicable multilayered nanofibrous patterns on a flexible film[J] .Langmuir, 2010,26 (18): 14395-14399.) utilize parallel pole to receive the parallel-oriented electrostatic spinning fiber of one deck, by 90 ° of rotary flat column electrodes in same plane, continue to receive the parallel-oriented electrostatic spinning fiber of one deck, the final tunica fibrosa that just obtains right-angled intersection orientations, and use as flexible insulator.Yang etc. (Yang X, Wang H.Electrospun functional nanofibrous scaffolds for tissue engineering[J] .Tissue Engineering.InTech; Croatia, 2010:159-176.) tunica fibrosa of the right-angled intersection orientations that makes in conjunction with electrostatic spinning and laminated assembling technology, and for field of tissue engineering technology.(the Tong H W such as Tong, Wang M, Lu W W.Electrospun poly (hydroxybutyrate-co-hydroxyvalerate) fibrous membranes consisting of parallel-aligned fibers or cross-aligned fibers:characterization and biological evaluation[J] .Journal of Biomaterials Science, Polymer Edition, 2011, 22 (18): 2475-2497.) use cylinder as receiving system, utilize auxiliary electrode to prepare the electrostatic spinning fiber film of right-angled intersection orientations, the tunica fibrosa that the fiber of right-angled intersection orientations is has good wettability, mechanical property, yet, the tunica fibrosa of preparation is but applied to cell proliferation field.
Summary of the invention
It is high that the present invention aims to provide a kind of intensity, has the preparation method of the electrostatic spinning nano fiber battery diaphragm of higher porosity, good wetting property concurrently.
Technical scheme provided by the invention is: a kind of two-way enhancement mode Static Spinning battery diaphragm, it is characterized in that, and described two-way enhancement mode Static Spinning battery diaphragm is a kind of three layers of composite cellulosic membrane.Wherein, lower floor, upper strata are random orientation tunica fibrosas, by parallel pole, under the plane low speed rotation state of electrode place, are being received and are obtaining; Intermediate layer is the tunica fibrosa of right-angled intersection orientations, by parallel pole after static reception a period of time again after 90 ° of electrode place Plane Rotations and static reception a period of time and obtaining.What prepare due to parallel pole is the fiber of parallel-oriented arrangement, therefore can on receiving screen, obtain orientations fibrage; After certain hour by parallel pole around 90 ° of electrode place Plane Rotations, just on original tunica fibrosa, receive again the fibrage that obtains parallel-oriented arrangement, two-layer orientations fibrage angle is about 90 °.By parallel pole, just obtain thus the tunica fibrosa of right-angled intersection orientations, and the tunica fibrosa of the right-angled intersection orientations obtaining is prepared to Static Spinning lithium ion battery separator as intermediate layer, its intensity longitudinally and laterally improves a lot.
This preparation method utilizes rotatable parallel pole to prepare the tunica fibrosa of right-angled intersection orientations, and improving Static Spinning lithium ion battery separator does not affect the basic structure of nano fiber porous film in length and breadth to mechanical strength, the performance of battery is improved.This barrier film porosity is up to 55-85%, and its tensile break strength improves 100-400% with respect to random orientation tunica fibrosa.This preparation process can complete on same electrostatic spinning apparatus, realizes composite diaphragm serialization and produces, and technique is simple, controls easily, and easy to operate, cost is low.
In the present invention program, the preparation method of described two-way enhancement mode Static Spinning lithium ion battery separator, comprises the following steps:
1) a kind of high molecular polymer is joined in organic solvent, mechanical agitation is dissolved, and forms the solution system of stable homogeneous, makes electrostatic spinning liquid;
2) another kind of high molecular polymer is joined in organic solvent, mechanical agitation is dissolved, and forms the solution system of stable homogeneous, makes electrostatic spinning liquid;
3) by 1) in preparation spinning solution electrostatic spinning prepare lower floor's nano fibrous membrane; Again by 2) the middle spinning solution electrostatic spinning of preparing deposits on lower floor's nano fibrous membrane, is intermediate layer; Finally, on intermediate layer, receive one deck upper strata electrostatic spinning nano fiber film, make three layers of composite cellulosic membrane, be two-way enhancement mode Static Spinning lithium ion battery separator.
Preferably, described 1) or 2) in high molecular polymer be one or more mixture of polymethyl methacrylate (PMMA), Kynoar (PVDF), Kynoar-hexachloropropylene copolymer (PVDF-HFP), polypropylene fine (PAN), polyoxyethylene (PEO), PETG (PET).
Preferably, described 1) or 2) in high molecular polymer organic solvent used be N, the mixture of one or two or more kinds in dinethylformamide, DMA, acetone, 1-METHYLPYRROLIDONE, hexafluoroisopropanol, oxolane, trifluoroacetic acid, carrene.
Preferably, the preparation method of described two-way enhancement mode Static Spinning lithium ion battery separator, is characterized in that: described solution concentration is 8-20wt%, and high-voltage power voltage is 15-35KV, and syringe pump flow velocity is 0.1-1.5ml/h, and receiving range is 10-35cm.
Preferably, the preparation method of described two-way enhancement mode Static Spinning lithium ion battery separator, is characterized in that: described upper and lower layer tunica fibrosa received and obtain under the Plane Rotation state of electrode place by parallel pole, and rotational line speed is 2-15m/min; Intermediate layer tunica fibrosa adopts parallel pole static reception a period of time and obtaining also after 90 ° of electrode place Plane Rotations again after static receptions a period of time.
Preferably, described 3) in, the thickness of two-way enhancement mode Static Spinning lithium ion battery separator is 20-40 μ m, and wherein intermediate layer thickness accounts for the 1/3-2/3 of gross thickness.
For achieving the above object, electrostatic spinning device of the present invention is comprised of three parts: control system 1, electrostatic spinning system 2, auxiliary system, wherein, control system 1 comprises spinning control unit, temperature and humidity regulation unit, drying configuration control unit, membrane winding control unit, drive motors speed adjustment unit, slide rail variable-speed unit, electrostatic spinning system 2 comprises high-voltage DC power supply 3, syringe pump 4, spinning head 5, move back and forth slide rail 6, slide rail 7, slide rail 8, electrode group 9, receiving screen 10, drive motors 11, auxiliary system comprises humiture monitoring device 12, solvent recovery unit 13, drying shaping equipment 14, membrane winding device 15, it is characterized in that: spinning head 5 is connected with positive high voltage or the negative high voltage of high-voltage DC power supply 3 one end outputs by wire, and electrode group 9 is connected with the ground wire of the high-voltage DC power supply other end by wire, 9 effective groundings of electrode group, and the drive motors drive electrode group place Plane Rotation that is connected with electrode group, the charging hole of spinning head 5 is connected with syringe pump 4 by pipeline, and spinning head 5 is connected with line slide rail 6,7,8 respectively.Control system 1 is the circuit master control case of package unit, can carry out the setting of device runtime parameter, wherein: spinning control unit can be controlled high-voltage DC power supply 3 and change spinning voltage, control slide rail 7 and change receiving range, control drive motors 11 and change electrode group rotary speed, control slide rail 6 and 7 and change spinning head 5 sweep speeds, control syringe pump 4 and change flow velocity; Temperature and humidity regulation unit regulates according to the humiture in 12 pairs of electrostatic spinning systems 2 of humiture monitoring device, keeps the stable of spinning environment; Drying configuration control unit is by controlling the drying temperature of barrier film, the tension force of barrier film to drying shaping equipment 14, and the evenness of membrane surface; Membrane winding control unit is collected prepared barrier film by controlling membrane winding device 15, reaches quantity-produced requirement.
Preferably, described preparation facilities, is characterized in that: described spinning head is flat mouth single needle spinning head or flat mouth spininess spinning head, and spinning head aperture is 0.5-1.2mm, and it is 10-60cm/min that spinning head moves back and forth speed.
Preferably, described preparation facilities, is characterized in that: described spininess spinning head number >=2, and for array distributes, two adjacent spinning head spacings are 18-60mm.
Preferably, described preparation facilities, it is characterized in that: described number of poles >=2, between two electrodes, be parallel to each other, two adjacent interelectrode distances are 2-10cm, electrode length is consistent with the interelectrode distance of head and the tail, and electrode 5 can be around electrode place Plane Rotation, and electrode place plane and receiving screen keeping parallelism.
Compared with prior art, two-way enhancement mode Static Spinning lithium ion battery separator provided by the present invention not only has lower percent thermal shrinkage that random orientation Static Spinning lithium ion battery separator has, good electrochemical stability and higher porosity, also has the following advantages:
1. the fiber cross arrangement of the Static Spinning lithium ion battery separator of preparation by orientations reaches in length and breadth to the object strengthening, and strengthens successful, can meet the requirement of battery pack process of assembling.
2. if upper, middle and lower layer all adopts same polymer spinning moulding, just by regulating parallel pole rotating speed can obtain the enhancement mode Static Spinning lithium ion battery separator of one-component; If upper, middle and lower layer adopts two kinds or two or more polymer, just can obtain multi-component enhancement mode Static Spinning lithium ion battery separator.
3. the Static Spinning lithium ion battery separator of spinning solution and preparation, without any processing, can directly obtain enhancing effect.
4. the present invention is when preparing battery diaphragm intermediate layer, can change the angle of rotating around rotating shaft (as: half-twist is adjusted into 5 °, 10 °, 30 ° or 60 ° of rotations) of parallel pole, and adopt suitable polymer to carry out electrostatic spinning, just obtain out different directions or even all directions tunica fibrosa that all crossed orientation is arranged, thereby prepare multi-direction even isotropic enhancement mode Static Spinning lithium ion battery separator.
5. the present invention directly prepares enhancement mode Static Spinning lithium ion battery separator by receiving system structure and the speed of service thereof, and process operation is easy, flow process is short.
Test shows, adopts enhancement mode electrostatic spinning nano fiber film prepared by the present invention to improve 100-400% than random orientation electrostatic spinning fiber film tensile break strength.
Accompanying drawing explanation
The two-way enhancement mode Static Spinning of Fig. 1 lithium ion battery separator structural representation: lower floor, upper strata are random orientation tunica fibrosa, intermediate layer is right-angled intersection orientations tunica fibrosa.
The preparation facilities of the two-way enhancement mode Static Spinning of Fig. 2 lithium ion battery separator.
Fig. 3 receiving system is the electrostatic spinning apparatus design sketch of parallel pole: (a) static parallel pole is prepared the fiber arranged film of axial orientation, (b) after parallel pole half-twist, obtains right-angled intersection orientations tunica fibrosa.
In figure, the implication of each Reference numeral representative is specific as follows: 1. control system, 2. electrostatic spinning system, 3. high-voltage DC power supply, 4. syringe pump, 5. spinning head group, 6. move back and forth slide rail, 7. slide rail, 8. slide rail, 9. electrode group, 10. receiving screen, 11. drive motors, 12. humiture monitoring devices, 13. solvent recovery units, 14. drying shaping equipments, 15. membrane winding devices.
Embodiment
Provide specific embodiments of the invention below.These specific embodiments, only for further narration the present invention, do not limit the claim protection range of the present patent application.
Embodiment 1
Kynoar (PVDF) is dissolved in to DMF (DMF) and acetone quality ratio=5: in 5 mixed solvent, be mixed with the solution that concentration is 12wt%, heating is stirred to abundant dissolving at 50-60 ℃.Solution is injected in the syringe pump with flat mouth syringe needle, and syringe needle connects high-voltage output end, and setting high-voltage DC power supply voltage is 15KV, and syringe pump flow velocity is 0.3ml/h, and receiving range is 15cm.Selecting number of poles is 4, and setting interelectrode distance is 2cm, and electrode length is 8cm; Select single needle spinning head, spinnerette diameters 0.5mm, it is 12cm/min that setting spinning head moves back and forth speed.Regulating parallel pole rotational line speed is 2m/min, polymer dope is prepared PVDF nano fibrous membrane through electrostatic spinning and is deposited on receiving screen, parallel pole is slowly adjusted to inactive state, after a period of time, PVDF orientation fibers is deposited on nano fibrous membrane, afterwards again by parallel pole half-twist and keep static a period of time, polymer dope is prepared PVDF nano fibrous membrane through electrostatic spinning and is deposited on PVDF orientation fibers, has obtained two-way enhancement mode Static Spinning battery diaphragm.
Test result show the two-way enhancement mode Static Spinning of PVDF battery diaphragm longitudinally and laterally tensile break strength with respect to random orientation tunica fibrosa, by 3.3MPa, be increased to 7.3MPa, approximately improve 121%.The porosity of two-way enhancing barrier film is about 84%.
Embodiment 2
Polyacrylonitrile (PAN) is dissolved in DMF (DMF), is mixed with the solution that concentration is 18wt%, at 65-75 ℃, heating is stirred to abundant dissolving.Solution is injected in the syringe pump with flat mouth syringe needle, and syringe needle connects high-voltage output end, and setting high-voltage DC power supply voltage is 25KV, and syringe pump flow velocity is 1.2ml/h, and receiving range is 25cm.Selecting number of poles is 10, and setting adjacent two interelectrode distances is 4cm, and electrode length is 40cm; Select 72 pin spinning heads, spinnerette diameters 0.7mm, two adjacent spinning head spacing 20mm, it is 20cm/min that setting spinning head moves back and forth speed.Regulating parallel pole rotational line speed is 5m/min, polymer dope is prepared PAN nano fibrous membrane through electrostatic spinning and is deposited on parallel pole receiving screen, parallel pole is slowly adjusted to inactive state, after a period of time, PAN orientation fibers is deposited on nano fibrous membrane, afterwards again by parallel pole half-twist and keep static a period of time, polymer dope is prepared PAN nano fibrous membrane through electrostatic spinning and is deposited on PAN orientation fibers, has obtained two-way enhancement mode Static Spinning battery diaphragm.
Test result show the two-way enhancement mode Static Spinning of PAN battery diaphragm longitudinally and laterally tensile break strength with respect to random orientation tunica fibrosa, by 3.5MPa, be increased to 17.3MPa, approximately improve 394%.The porosity of two-way enhancing barrier film is about 89%.
Embodiment 3
By in polymethyl methacrylate (PMMA) and the PVDF mixed solvent that to be dissolved in mass ratio with DMA and acetone quality ratio at 5: 5 be 7: 3, be configured to the solution of 10wt%, at 40-50 ℃, heating is stirred to polymer and fully dissolves.Mixed solution is injected in the syringe pump with flat mouth syringe needle, and syringe needle connects high-voltage output end, and setting high-voltage DC power supply voltage is 20KV, and syringe pump flow velocity is 1.0ml/h, and receiving range is 25cm.Selecting number of poles is 15, and setting two adjacent interelectrode distances is 6cm, and electrode length is 90cm; Select 210 pin spinning heads, spinnerette diameters 0.9mm, two adjacent spinning heads are apart from 30mm, and it is 35cm/min that setting spinning head moves back and forth speed.Regulating parallel pole rotational line speed is 13cm/min, polymer dope is prepared PMMA/PVDF nano fibrous membrane through electrostatic spinning and is deposited on parallel pole receiving screen, parallel pole is slowly adjusted to inactive state, PMMA/PVDF orientation fibers is deposited on nano fibrous membrane, afterwards again by parallel pole half-twist and keep static a period of time, polymer dope is prepared PMMA/PVDF nano fibrous membrane through electrostatic spinning and is deposited on PMMA/PVDF orientation fibers, has obtained two-way enhancement mode Static Spinning battery diaphragm.
Test result show the two-way enhancement mode Static Spinning of PMMA/PVDF battery diaphragm longitudinally and laterally tensile break strength with respect to random orientation tunica fibrosa, by 2.4MPa, be increased to 8.7MPa, approximately improve 263%.The porosity of two-way enhancing barrier film is about 84%.
Embodiment 4
Kynoar (PVDF) is dissolved in to DMF (DMF) and acetone quality ratio=5: in 5 mixed solvent, be mixed with the solution that concentration is 12wt%, heating is stirred to abundant dissolving at 50-60 ℃.Polyacrylonitrile (PAN) is dissolved in DMF (DMF), is mixed with the solution that concentration is 18wt%, at 65-75 ℃, heating is stirred to abundant dissolving.PVDF solution is injected in the syringe pump with flat mouth syringe needle, and syringe needle connects high-voltage output end, and setting high-voltage power voltage is 15KV, and syringe flow velocity is 0.3ml/h, and receiving range is 15cm.Selecting number of poles is 20, and setting adjacent two interelectrode distances is 80mm, and electrode length is 160cm; Select 380 pin spinning heads, spinnerette diameters 1.1mm, two adjacent spinning heads are apart from 40mm, and it is 55cm/min that setting spinning head moves back and forth speed.Regulating parallel pole rotational line speed is 15m/min, and polymer dope is prepared PVDF nano fibrous membrane through electrostatic spinning and is deposited on receiving screen; PAN solution is injected in another syringe pump with flat mouth syringe needle, and syringe needle connects high-voltage output end, at the other end apart from syringe needle 25cm, is the parallel pole with high-voltage DC power supply ground connection.Regulating the injection speed of syringe pump is 1.2ml/h, slowly boosted voltage is to 25kv, slowly regulate parallel pole to static, after a period of time, PAN orientation fibers is deposited on PVDF nano fibrous membrane, afterwards by parallel pole half-twist and keep static a period of time, PVDF solution is prepared PVDF nano fibrous membrane through electrostatic spinning and is deposited on PAN orientation fibers, has obtained two-way enhancement mode Static Spinning battery diaphragm.
Test result show the two-way enhancement mode Static Spinning of PVDF/PAN/PVDF battery diaphragm longitudinally and laterally tensile break strength with respect to random orientation tunica fibrosa, by 3.8MPa, be increased to 14.8MPa, approximately improve 289%.The porosity of two-way enhancing barrier film is about 80%.
Claims (11)
1. a two-way enhancement mode Static Spinning lithium ion battery separator, is characterized in that, described two-way enhancement mode Static Spinning lithium ion battery separator is a kind of three layers of composite cellulosic membrane; Lower floor, upper strata are random orientation tunica fibrosas, by parallel pole, under the Plane Rotation state of electrode place, receive and obtain, intermediate layer is the tunica fibrosa of right-angled intersection orientations, by parallel pole after static reception a period of time again after 90 ° of electrode place Plane Rotations and static reception a period of time and obtaining, and intermediate layer accounts for the 1/3-2/3 of gross thickness; This barrier film porosity is up to 55-85%, and its tensile break strength has improved 100-400% with respect to random orientation tunica fibrosa.
2. the preparation method of two-way enhancement mode Static Spinning lithium ion battery separator claimed in claim 1, is characterized in that, concrete steps are:
The first step: a kind of high molecular polymer is joined in organic solvent, and mechanical agitation is dissolved, and forms the solution system of stable homogeneous, makes electrostatic spinning liquid;
Second step: another kind of high molecular polymer is joined in organic solvent, and mechanical agitation is dissolved, and forms the solution system of stable homogeneous, makes electrostatic spinning liquid;
The 3rd step: spinning solution electrostatic spinning in the first step is prepared to lower floor's nano fibrous membrane; Spinning solution electrostatic spinning in second step being deposited on lower floor's nano fibrous membrane, is intermediate layer again; Finally, on intermediate layer, receive one deck upper strata electrostatic spinning nano fiber film, make three layers of composite cellulosic membrane, be two-way enhancement mode Static Spinning lithium ion battery separator.
3. preparation method claimed in claim 2, it is characterized in that, the high molecular polymer in the described first step and second step is one or more mixture of polymethyl methacrylate (PMMA), Kynoar (PVDF), Kynoar-hexachloropropylene copolymer (PVDF-HFP), polypropylene fine (PAN), polyoxyethylene (PEO), PETG (PET).
4. preparation method claimed in claim 2, it is characterized in that, high molecular polymer organic solvent used in the described first step and second step is N, the mixture of one or two or more kinds in dinethylformamide, DMA, acetone, 1-METHYLPYRROLIDONE, hexafluoroisopropanol, oxolane, trifluoroacetic acid, carrene.
5. barrier film preparation method claimed in claim 2, is characterized in that, described solution concentration is 8-15wt%, and high-voltage power voltage is 15-35KV, and syringe flow velocity is 0.1-1.5ml, and receiving range is 10-35cm.
6. preparation method claimed in claim 2, is characterized in that, described San Buzhong lower floor, upper strata are random orientation tunica fibrosas, by parallel pole, under the plane low speed rotation state of electrode place, are being received and are obtaining, and parallel pole rotational line speed is 2-15m/min; Intermediate layer is the tunica fibrosa of right-angled intersection orientations, by parallel pole after static reception a period of time again after 90 ° of electrode place Plane Rotations and static reception a period of time and obtaining.
7. preparation method claimed in claim 6, it is characterized in that, described static parallel pole adaper is first received and is obtained the tunica fibrosa that axial orientation is arranged, by receiving in orientations direction perpendicular to axial direction after parallel pole half-twist, to obtain another layer of axial orientation fiber arranged, thereby obtain the fibrage of right-angled intersection orientations; And rotary flat column electrode receives the tunica fibrosa that obtains random orientation arrangement; The right-angled intersection orientations of fiber has improved Static Spinning battery diaphragm at vertical and horizontal tensile break strength.
8. the preparation facilities of two-way enhancement mode Static Spinning lithium ion battery separator claimed in claim 1, is characterized in that, the electrostatic spinning device adopting is comprised of three parts: control system, electrostatic spinning system, auxiliary system, wherein, control system comprises spinning control unit, temperature and humidity regulation unit, drying configuration control unit, membrane winding control unit, drive motors speed adjustment unit, slide rail variable-speed unit, electrostatic spinning system comprises high-voltage DC power supply, syringe pump, spinning head, move back and forth slide rail, slide rail, slide rail, electrode group, receiving screen, drive motors, auxiliary system comprises humiture monitoring device, solvent recovery unit, drying shaping equipment, membrane winding device, it is characterized in that: spinning head is connected with positive high voltage or the negative high voltage of the output of high-voltage DC power supply one end by wire, and electrode group is connected with the ground wire of the high-voltage DC power supply other end by wire, the effective grounding of electrode group, and the drive motors drive electrode group place Plane Rotation that is connected with electrode group, the charging hole of spinning head is connected with syringe pump by pipeline, and spinning head is connected with line slide rail.
9. preparation facilities claimed in claim 8, it is characterized in that, described number of poles >=2, between two electrodes, be parallel to each other, two adjacent interelectrode distances are 2-10cm, electrode length is consistent with the interelectrode distance of head and the tail, and electrode can be around electrode place Plane Rotation, and electrode place plane and receiving screen keeping parallelism.
10. preparation facilities claimed in claim 8, is characterized in that, described spinning head is flat mouth single needle spinning head or flat mouth spininess spinning head, and spinning head aperture is 0.5-1.2mm, and it is 10-60cm/min that spinning head moves back and forth speed.
11. preparation facilitiess claimed in claim 10, is characterized in that, described spininess spinning head number >=2, and for array distributes, two adjacent spinning head spacings are 18-60mm.
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